Process for forming films and filaments



Aug. 25, 1959 c. R. KOLLE Re. 24,689

R PROCESS FOR FORMING FILMS AND FILAMENTS DIRECTLY FROM POLYMERINTERMEDIATES Original Filed Feb. 21, 1955 I INVENTOR CHARLES KOLLERUnited States Patent OfiFice Re. 24,589 Reissued Aug. 25, 1959 PROCESSFOR FORMING FILMS AND FILAIVIENTS DIRECTLY FROM POLYMER INTERIVIEDIATESCharles R. Koller, Wilmington, Del., assignor to E. L du Pont de Nemonrsand Company, Wilmington, DeL, a corporation of Delaware Original No.2,813,776, dated November 19, 1957, Serial No. 489,584, February 21,1955. Application for reissue November 2'5, 1958, Serial No. 776,667

20 Claims. (Cl. 18-54) Matter enclosed in heavy brackets appears in theoriginal patent but forms no part of this reissue specification; matterprinted in italics indicates the additions made by reissue.

This invention relates to a process. More particularly it concerns aprocess for forming a shaped body having a continuous cross section, bycombination of two'liquid complementary reactive polymer intermediates,the said combination being accomplished by extruding one of the saidintermediates into the other.

It is an object of the present invention to provide a process for theproduction of a shaped body of continuous cross section by combinationof two liquid complementary reactive polymer intermediates.

Another object is to provide a process for the production of an elasticshaped body of continuous cross section by combination of two liquidcomplementary reactive polymer intermediates.

These and other objects will become apparent in the course of thefollowing specification and claims.

In accordance with the present invention a process is provided whichcomprises forming a solid shaped structure by combining at least twoliquid complementary reactive polymer intermediates, one of whichcontains at least two active hydrogens more reactive than alcoholichydrogen, whereas its complement contains at least two reactive groupscapable of reacting with alcohol at room temperature to form an ester,and at least one of the said complementary reactive polymerintermediates being a multifunctional organic macromolecule, having amolecular weight within the range of from about 400 to about 7000, thesaid macromolecule consisting essentially of at least one memberselected from the group consisting of a hydrocarbon polymer, a polyetherand a polythioether,

and at least one of the other of the said complementary reactive polymerintermediates being a polyfunctional, essentially monomeric, organicmolecule, the proportionate molecular weights of macromolecularintermediate to the essentially monomeric molecular intermediate beingsuch that at least about 30% by weight of the final shaped structure iscontributed by the macromolecular intermediate [While at least about byWeight of the final shaped structure is contributed by the essentiallymonomeric molecular intermediate], the combination of the saidcomplementary intermediates being accomplished by extrusion through anorifice of one said complementary polymer intermediate into the other.

The liquid complementary reactive polymer intermediates correspond tothe formulae:

wherein n is a small integer greater than 1, X is hydrogen more activethan alcoholic hydrogen, Y is a group capable of reacting with alcoholat room temperature to form an ester, R and R are members of the classconsisting of the radical of a polyfunctional essentially monomericorganic polymer intermediate and the radical of a polyfunctionalmacromolecular polymer intermediate havinga molecular weight range offrom about 400 to about 7000 and consisting essentially of a hydrocarbonpolymer, a polyether and a polythioether. As previously mentioned, inthe process of the present invention, the complementary reactive polymerintermediates are so chosen that at least 30%, preferably 60% of theweight of the final shaped article is contributed by the polyfunctionalorganic macromolecule [whereas at least 10% of the weight of the finalshaped article is contributed by the polyfunctional, organic,essentially monomeric molecule].

By the expression a shaped body of continuous cross section is meant asolid structure in the nature of a filament or film whose cross sectionis uniform and unbroken as opposed to structures which have soft orhollow centers. The terms monomeric and essentially monomeric are usedinterchangeably to signify a monomer or a polymer having a low degree ofpolymerization, i.e., dimer, trimer, etc. The term polyfunctionalindicates the presence upon the molecule of at least two reactive groupscapable of reaction with a complementary functionally substitutedmolecule to form a polymer under conditions of the present invention.The expression polymer intermediate denotes a molecule polyfunctionallysubstituted and capable of reacting with a complementarypolyfunctionally substituted molecule to form a polymer under reactionconditions of the present invention.

Figure l is an illustration of a cross-sectional element of a filamentprepared in accordance with the present invention.

Figure 2 is a diagrammatic sketch of the typical spinning set-up of thepresent invention.

In Figure 2 one of the reactive intermediates is supplied through thesupply tube 2 and extruded through the orifice 3 into the othercomplementary reactive polymer intermediate 1. The filament 4 which isformed by the reaction of the two intermediates is then led around therollers 5 and 6 to be wound in the conventional manner.

The following examples are cited toillustrate the invention. They arenot intended to limit it in any manner. Among the physical propertiesreported for the products in the examples, polymer melt temperature isthe minimum temperature at which a sample of the polymer leaves a Wet,molten trail as it is stroked with moderate pressure across a smoothsurface of a heated brass block. Fiber stick temperature is thetemperature at which the fiber will just stick to a heated brass blockwhen held against the surface of the block for 5 seconds with a 200 gramweight. Zero strength temperature is the average temperature at whichthe two ends of the fiber break if heating is continued with the weightleft on after the fiber stick temperature has been determined. Initialmodulus is determined by measuring the initial slope of the stressstrain curve. The invention has particular value in the preparation ofarticles having high elasticity. In reporting this property thosestructures are included which exhibit elastic recoveries above andstress decays below 20%. Elastic recovery is the percentage return tooriginal length within one minute after the tension has been releasedfrom a sample which has been elongated 50% at the rate of per minute andheld at 50% elongation for one minute. Stress decay is the percent lossin stress in a yarn one minute after it has been elongated to 50% at therate of 100% per minute.

EXAMPLE I A poly(tetramethylene oxide) glycol with a molecular weight of3300 and prepared as described in the literature 7 3 mol of the glycolwith two mols of 4-methyl-m-phenylene diisocyanate. The reactants areheated at 80 C. for 4 hours with stirring to produce a syrupy liquidwith a viscosity of 350 poise at room temperature. This syrupy liquid isextruded through a 6 mil one-hole spinneret into a xylene bathcontaining 5% by Weight of triethylenetetramine heated to 70 C. Thefilament is wound up at 77 feet per minute and air dried, The as-spunfilaments have the following properties: Tenacity=0.26 g.p.d.,elongation=704%, initial modulus=0.02 g.p.d., denier=86.

EXAMPLE II A macroglycol is prepared by mixing 333 grams (3.7 nols) of1,4-butanediol, 452. grams (3.7 mols) of by droxyethylthioether, 15grams of p-toluenesulfonic acid as catalyst, and 150 ml. of toluene,blanketing with nitrogen, and refluxing for 5.5 hours while removingwater azeotropically. The reaction mixture is washed with 600 ml. of anaqueous 5% sodium carbonate solution and then with 600 ml. of water. Theproduct is further purified by dissolving in- 500 ml. of benzene,treating with 50 grams of alumina, filtering, redissolving the filtratein benzene, treating with an activated carbon, and filtering. Thesolvent is removed from the filtrate under vacuum on the steam bathuntil the final pressure reaches 0.5 mm. The product contains 2.03%hydroxyl groups and has an average molecular weight of 1675.

This product (20.0 grams=0.012 mol) is mixed with 2.41 grams (0.024 mol)of triethylamine and 20 ml. of dry benzene and the mixture added over aperiod of 12 minutes to a solution of 5.70 grams of sebacyl chloride in20 ml. of dry benzene. The reaction mixture is allowed to stand for fourhours at room temperature.

It is filtered and sufficient dry benzene added to give a total volumeof solution of 60 ml.

This macrointermediate having acid chloride ends is extruded through aone-hole spinneret into liquid triethylenetetramine at room temperature.Clear, lustrous filaments are obtained.

EXAMPLE III p,p'-Methylenediphenylisocyanate (10.6 grams=0.042 mol) isheated with 50 grams (0.016 mol) of Tetronic (a tetrahydroxypolyetherfrom Wyandotte Chemicals) in 25 ml. of dioxan for one hour at steam bathtemperatures. The reaction mixture is extruded through an .8 mil oneholespinneret at 240 p.s.i. into a 100% ethylenediamine bath maintained atroom temperature. The filaments obtained are removed from the bath at 30feet per minute and transferred through air to a second roll, whichtakes up the filaments at 58 feet per minute. wound up at 48 feet perminute on a bobbin immersed in water. After relaxing in boiling water,the as-spun filaments have the following properties: Tenacity=0.08g.p.d., elongation=96%, initial modulus=0.05 g.p.d., denier=129, stressdecay=1.8%, tensile recovery=99%, and fiber stick temperature=2l0 C.

EXAMPLE IV Poly(tetramethylene oxide) glycol (56.7 grams=.0.a036

of 46 feet per minute on a bobbin immersed in water.

After relaxing in boiling water, the as-spun filaments have thefollowing properties: Tenacity=0.63 g.p.d., elongation=542'%, initialmodulus=0.05 g.p.d., denier=66, stress decay=5.-9% and tensilerecovery=96'-%.

They are then EXAMPLE V Chlorosulfonated polyethylene (Hypalon 1287".achlorosulfonated polyethylene supplied by the Du Pont Company) isdissolved in toluene to produce a solution containing 25% solids, whichis extruded into 100% triethylenetetramine at room temperature. Thesolution is extruded through an 8 mil one-hole spinneret under apressure of 110 p.s.i., and the filament is wound up at 44 feet perminute. After being washed in acetone and dried, the as-spun filamenthas the following properties: Tenacity=0.3 g.p.d., elongation=1l0%,initial modulus=0.07 g.p.d., and denier=83.

EXAMPLE VI Ethyl acrylate grams), acrylyl chloride (10 grams) and adiazo catalyst (1 gram) are mixed with 200 ml. of benzene and thesolution refluxed for 9 hours. Excess solvent is removed to give aviscous solution of the copolymer, which is extruded through an 8 milone-hole spinneret into an 86% aqueous solution of hexamethylenediaminemaintained at room temperature. Continuous filaments are obtained whichare insoluble in boiling benzene.

EXAMPLE VII Poly(ethylene oxide) glycol with a molecular weight of 400is reacted with excess phosgene to produce the hischloroformate. Acarbon tetrachloride (50 ml.) solution containing 21 grams of thisproduct per ml. of solution is mixed with 50 ml. of carbon tetrachloridesolution containing 10 grams of sebacyl chloride per hundred ml. ofsolution. The combined solutions are extruded through an 8 mm. orificeinto an aqueous bath containing 5% "by weight of hexamethylenediamine.The filaments are withdrawn from the bath at 15 feet per minute andwound up at 30 feet per minute in methanol at 40 C. The dry filamentscan be drawn at 2.5X at 90 C. and have a zero strength temperature of186 C. The polytiter in these filaments has an inherent viscosity in m--.Furthermore, the polymeric product, regardless of its variety oflinkage, may be of a coupled type, i.e. only one of each of twocomplementary intermediates is used in its production, or segmented,i.e. a mixture of at least two homofunctional species of oneintermediate is reacted with one or more species of complementaryhomofunctional intermediates. In the formation of the segmented productsthe speed of reaction between the various complementary intermediates ispreferably substantially equal. It is preferable that the speed ofreaction of the fastest reacting complementary intermediates be close tothe speed of reaction of the slowest reacting complementaryintermediates in any particular system.

The invention is particularly useful in the preparation of shapedarticles possessing elasticity. The degree of elasticity will varysomewhat with the identity of the complementary polymer intermediates.

The effect of the macromolecular polymer intermediates is particularlypronounced in this regard. In general, highly elastic products may beformed with macromolecular intermediates having a molecular weight inthe lower end of the range specified, i.e., around 400, provided theproduct is cross-linked or segmented with units of polymer derived fromessentially monomeric polymer intermediates. A macromolecularintermediate of somewhat higher molecular weight, around 800, ispreferable, when the product formed is a linear coupled polymer. The useof a macromolecular intermediate havinga melting point no higher thanabout 50 C. is particularly advantageous in imparting elasticity to thefinal product.

The elastic properties of the structures obtained is varied to a lesserextent by the essentially monomolecular intermediates. This appliesparticularly to the structures derived from linear polymers prepared bythe process of the invention. For example, if each reaction phasecontains an essentially monomeric intermediate in addition to themacromolecular intermediate (present with at least one essentiallymonomeric intermediate) the product obtained will be a segmentedcopolymer as previously defined. For optimum elastic properties of suchstructure it is preferred that these two complementary essentiallymonomeric intermediates be capable of reacting together to form apolymer with a polymer melt temperature above 200 C. in thefiber-forming molecular weight range. The higher the melting point ofthis segment, the closer the molecular weight of the macromolecularintermediate can approach the minimum value and still retain excellentelasticity. If the reactive macromolecular intermediate is extruded intoa liquid comprising only one complementary, essentially monomericfast-reacting intermediate, then it is preferred that this essentiallymonomeric intermediate be capable of reaction with the end groups of themacromolecular intermediate to form a polymer which melts above 250 C.in the fiber-forming molecular weight range. The variation of elasticitycaused by the character of the essentially monomolecular intermediate,as mentioned above, is much less pronounced when crosslinked structuresare prepared. However, generally it is preferred that the finalstructure contain only a small number of cross-links per molecule. Thiscan be accomplished by using a relatively high molecular weightmacromolecular intermediate (one having a molecular weight in the rangeof about 3000 to about 5000) or by using at least two complementaryessentially monomeric intermediates, one of which is difunctional andone of which is multifunctional, the latter representing a smallpercentage of the mixture.

The use of a macromolecular intermediate having a molecular' weightabove the indicated minimum values has an advantage due to the fact thata high molecular weight fiber-forming polymer is obtained by combinationof a relatively small number of molecules. As a result, little byproduct is formed, particularly where polymerization proceeds bycondensation. This simplifies threadline formation and attendantpurification processes. Furthermore, high solids spinning dopes (i.e.the material extruded) can be used, which reduces solvent removal andrecovery problems. An important end result is the ready formation ofsolid structures, such as filaments and films, rather than collapsedtubular filaments or laminated films. For these reasons the use of atleast one macromolecular intermediate having a molecular weight of about1000 to about 5000 is preferred.

The liquid complementary reactive polymer intermediates are combined inaccordance with the present invention, by extruding at least one suchintermediate through an orifice into its complement and the shapedarticle formed is led away from the orifice as it forms to a reel orother suitable conventional Wet-processing collecting means. Generallyit is preferred to extrude the phase containing the macromolecularintermediate. For spinning fibers extrusion may be through aconventional wetspinning spinneret. A spinneret providing an orifice ofabout 3 to about mils is preferred although orifices of larger diametermay be employed. Furthermore, orifices of shapes other than round aresuitable. A slotted orifice may be used to produce films and ribbons.The shaped article may be washed, stretched, lubricated or otherwiseafter-treated.

Preferably each complementary reactive intermediate is, a liquid underthe conditions of the reaction or is dissolved in a liquid diluent.However, one of the said intermediates may be a finely divided soliddispersed in a liquid in which it is at least partially soluble. Whendiluents are employed it is preferred that the total concentration ofthe extruded intermediate be at least about 35% by'weight of extrudedmaterial. Use of higher concentrations promotes compactness of thepolymeric structure and reduces the problems associated with handlinglarge volumes of solvents, particularly the organic solvents, which tendto be toxic, expensive, inflammable, etc. Satisfactory solid productscan be obtained by using lower concentrations for some sets ofcomplementary intermediates.

The speed at which the formed solid shaped products can be collectedwill depend upon the specific reactants and reaction conditions, such asthe diluents used and the concentration of the reactants in thesediluents. Much of the influence exerted by the diluents appears to liein their effect upon the base strength of the intermediate reactantwhich is to act as a proton donor in the reaction. For example, theeifect is quite marked when water is used as a diluent, but inertdiluents for diamines, such as benzene and dioxan, appear to exertlittle noticeable effect on the course of the reactions involved in thisprocess. Additional functions of the diluents are to control theviscosity of the phases and the interfacial tension be tween theextruded phase and the bath. For example, it has been noted that theaddition of low percentages of N,N-dimethylformamide to viscous spindopes permits better penetration by the bath and results in highertenacities.

Useful inert diluents for diamines include dioxan, benzene,tetrahydrofuran, and the like. Suitable inert materials for dilutingacid halides, such as acid chlorides and chloroformates, includebenezene, toluene, xylene, cyclohexane, trichloroethylene,chlorobenzene, nitrobenzene, heptane, isooctane, diethyl ether, ethylacetate, methyl amyl ketone, ethylene dichloride, carbon tetrachloride,chloroform, etc. It is essential that the diluents be materials which donot react as readily with either polymerforming intermediate as does itscomplementary intermediate, and thus reduce the probability of polymerformation.

While it is sometimes desirable to add an acid acceptor to a systemwhich involves a reaction between a diacid halide and a coreactant, itis not necessary to do so. The particular advantage in using about anequivalent of alkali per equivalent of diamine in the bath is that itregenerates the diamine from any amine hydrohalide that forms, andminimizes the recovery of diamine from bath liquors. The process isordinarily operated at room temperature, although temperatures rangingfrom 10 C. to C. have been used successfully.

As previously defined, one of the complementary polymer intermediatescontains at least two active hydrogens more reactive than alcoholichydrogen, i.e., the hydrogen of an alkanol. Among end groups providingsuch a hydrogen may be mentioned SH, phenolic-OH, amino-NHR (in which Ris H or alkyl) and amidino. The other complementary polymer intermediatecontains at least two reactive groups capable of reacting with alcoholto form an ester. Among such groups may be mentioned the acid chloridegroup, the chloroformate group and the isocyanate group. The use ofcomplementary polymer intermediates which form a self-supportingpolymeric structure Within 10 seconds after combination at roomtemperature is preferred. A large variety of suitable such combinationsis illustrated in copending US. application No. 226,066, filed May 12,1951, now Patent No. 2,708,617.

The multifunctional organic macromolecular intermediate consistsessentially of a member of the class consisting of a hydrocarbonpolymer, a polyether and a polythioether, equipped if desired ornecessary with functional end groups as required by the conditions ofthe reaction. Thus the carbon skeleton may be a hydrocarbon polymer,such as polyethylene, which has been provided with reactive groups by asuitable reaction, such as chlorosulfonation, as shown by Example V. Itis also possible to utilize polymers prepared from vinyl monomerscontaining groups which are not reactive under the conditions used, suchas the ester groups in vinyl acetate, by forming copolymers with vinylmonomers containing very reactive groups, such as the acid chloridegroups of acrlyl chloride. As is shown in Example VI, use of smallpercentages of the acid chloride in the copolymeric macrointermediatepermits formation of a final polymer containing sufiiciently fewcross-links that the shaped structures are readily deformable.Furthermore, -low molecular weight polyisoprene, polybutadiene, andsimilar derivatives terminated with amine groups can be utilized readilyin the process of the present invention. Representative macromolecularintermediates of this class are described more fully in US. 2,647,146.Another method of obtaining hydrocarbons with reactive ends is tooxidize butadiene-isobutylene copolymers containing small percentages'ofbutadiene with nitric acid. The products isolated are essentiallypolyisobutylene with carboxyl ends, which can be converted to acidhalides for use in thisprocess.

Representative polyethers which may be used include thepolyoxathiaalkylene glycols, such as poly( 1,6-dioxa-9- thiahendecane),poly(1,4-dioxa-7-thianonane), and poly- (l-oxa-4-thiahexane); theoly(alkylene oxide) glycols, such as poly(ethylene oxide) glycol,poly(propylene oxide) glycol, oly(tetramethylene oxide) glycol, andoly(decamethylene oxide) glycol; polydioxolane and polyformals preparedby reacting formaldehyde with other glycols or mixtures of glycols, suchas tetramethylene glycol and pentamethylene glycol, and copolyethersderived from more than one glycol. Some of the alkylene radicals inthese polyethers may be substituted by arylene and/or cycloaliphaticradicals. Multifunctional polyethers may also be used, as has beendemonstrated in the examples. Poly(propylene sulfide) may also be used.

Aliphatic glycols must be provided with hydrogen end groups which aremore reactive than the hydrogen of alcoholic hydroxyl or with an endgroup capable of reacting with alcohol at room temperature to form anester. Amine ends can be provided by reacting the glycols withacrylonitrile and reducing. The acid halide ends may be made by reactingthe glycol with two mols of a diacide halide. The chloroformate ends canbe produced by reacting the glycol with excess phosgene, and isocyanateends can be provided by reacting the glycol with a diisocyanate.

The polyfunctional essentially monomeric organic polymer intermediatemay be any polymer-forming molecule corresponding to the formulaewherein n is a small integer greater than 1, X is hydrogen more activethan alcoholic hydrogen, Y is a group capable of reacting with alcoholat room temperature to form an ester, Z is an organic radical and m is asmall number at least 1. Among such materials may be mentioned alkylenediamines such as ethylene diamine, propylene diamine, hexamethylenediamine, as well as phenylene diamine, diaminocyclohexane, diethylenetriamine, adipyl chloride, sebacyl chloride, terephthaloyl chloride,phenols such as resorcinol, the his chloroformates of the alkyleneglycols and the like.

The shaped bodies of the present invention are of continuous and uniformcross-section, i.e. they are solid without soft or open centers. Ingeneral, these strucs tures are relatively stable to hydrolysis underthe conditions used for commercial laundering. This is an importantattribute for fiilaments which are to be utilized in fabrics subject towashing. Most are more resistant to oxidation than are the conventionalelastic filaments. If desired, their stability can be improved by,incorporating commercially available antioxidants and ultra-violet lightstabilizers.

The high tenacity, high initial modulus, excellent abrasion resistance,and easily controlled elongation of the elastic structures prepared bythe process of this in vention fit them for many applications,particularly in film and filament form, for which rubber is undesirable.A particular advantage is that uncovered low denier multifilaments canbe used to prepare sheer elastic fabrics. An important additionaladvantage, particularly for filaments, is that solid structures areobtained by a simple process. A large percentage of the rubber threadsused are prepared by slitting rubber sheets. This Produces relativelylarge denier filaments, which cannot be converted readily intomultifilaments and are not acceptable for many uses, particularly incertain fabrics.

In general, the process of this invention provides a very useful toolfor preparing films and fibers comprising high molecular weightcondensation polymers. The process circumvents many of the normal stepsrequired for converting polymeric materials into useful shaped articles.It provides the only method for the preparation of shaped articles fromcertain polymeric materials, for example, those prepared fromintermediates that are unstable at the high temperatures normallyrequired in the condensation reaction. It provides a method forpreparing elastic polymers of sufficiently high molecular weight at roomtemperatures that the shaped articles are useful. Also, intermediateswhich would normally be too impure for conventional melt polymerizationcan be used. In addition, there is no need to maintain a delicatebalance of materials in order to obtain high molecular weight polymer,as is required by melt polymerization. There is also provided a newmethod for preparing films and filaments comprising certain cross-linkedpolymers.

Many equivalent modifications will be apparent to those Skilled in theart from a reading of the above description without a departure from theinventive concept.

What is claimed is:

1. A process which comprises forming a solid shaped structure bycombining at least two liquid complementary reactive polymerintermediates, one of which contains at least two active hydrogens morereactive than alcoholic hydrogen, whereas its complement contains atleast two reactive groups capable of reacting with alcohol at roomtemperature to form an ester, and at least one of said complementaryreactive polymer intermediates being a multifunctional organicmacromolecule, having a molecular weight within the range of from about400 to.

such that at least about 30% by weight of the final shaped structure iscontributed by the macromolecularintermediate [while at least about 10%by weight of the final shaped structure is contributed by the monomericmolecular intermediate], the combination of the said complementaryintermediates being accomplished by ex truding through an orifice onesaid complementary poly mer intermediate into the other.

2. The process of claim 1 wherein the macromolecular intermediatecomprises at least about 60% by weight of the final shaped article.

3. The process of. claim 1 wherein the extruded liquid contains amacromolecular intermediate.

4. The p oc 'of laim 1 wh rein he macromolecular intermedia e is ess n ly a hydr arbon Polymer.

5. The process of claim 1 wherein the macromolecular intermediate isessentially a polyether.

6. The process of claim 1 wherein the macromolecular intermediate isessentially a polythioether.

7. The process of claim 1 wherein the active hydrogens more active thanalcoholic hydrogen are supplied by a s mercaptan radical.

8. The process of claim 1 wherein the active hydrogens more active thanalcoholic hydrogen are supplied by a phenolic hydroxyl radical.

9. The process of claim 1 wherein the active hydrogens more active thanalcoholic hydrogen are supplied by an amino-NHR radical wherein R is amember of the class consisting of [hydrgoen] hydrogen and alkyl.

10. The process of claim 1 wherein the active hydrogens more active thanalcoholic hydrogen are supplied by an amidino radical.

11. The process of claim 1 wherein the reactive groups capable ofreacting 'with alcohol at room temperature to form an ester are acidchloride.

12. The process of claim 1 wherein the reactive groups groups capable ofreacting with alcohol at room temperature to form an ester are carbonylchloride.

13. The process of claim 1 wherein the reactive groups 10 a capable ofreacting with alcohol at room temperature to form an ester arechloroformate.

14. The process of claim 1 wherein the reactive groups capable ofreacting with alcohol at room temperature to form an ester areisocyanate.

15. The process of claim 1 wherein the complementary reactiveintermediates combine to form an amide.

16. The process of claim 1 wherein the complementary reactiveintermediates combine to form a urethane.

17. The process of claim 1 wherein the complementary reactiveintermediates combine to form a urea.

18. The process of claim 1 wherein the complementary reactiveintermediates combine to form an ester.

19. The process of claim 1 wherein the complementary reactiveintermediates combine to form a sulfonamide.

20. The process of claim 1 wherein each complementary reactiveintermediate contains only two reactive groups.

References Cited in the file of this patent or the original patentUNITED STATES PATENTS 2,708,617 Magat May 17, 1955

